Abstract
The topological and orbital symmetry constraints governing the intramolecular rearrangements of closo -polyhedral borane anions have been analysed. If the diamond-square-diamond rearrangement process occurs through an intermediate of C 4 v symmetry it corresponds to a pseudo-90° rotation of the polyhedron. For deltahedra such an intermediate is only possible if there are a total of 4 p +1 ( p = 1, 2,...) boron atoms. These rearrangements are orbitally forbidden and consequently have high activation energies, e.g. B 5 H 2− 5 - and B 9 H 2− 9 -. If the diamond-square-diamond rearrangement proceeds through a C 2 v or C s intermediate it corresponds to a pseudo-reflection of the polyhedron and the process is symmetry allowed. Such symmetry allowed processes can occur for B 8 H 2− 8 and B 11 H 2− 22 .
Published Version
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